Process of making indoxylic compounds.



UNITED STATES Patented October 18, 1904.

PATENT OFFICE.

VVILHELM BEHAGHEL AND GUSTAV CURT SCHUMANN, OF LUDVVIGS- HAFEN-ON-THE-RHIN I, GERMANY, ASSIGNORS TO BADISCHE ANILIN & SODA FABRIK, OF LUDVVIGSHAFEN-ON-THE-RHINE, GERMANY, A

CORPORATION OF BADEN.

PROCESS OF MAKING INDOXYLIC COMPOUNDS.

SPECIFICATION forming part of Letters Patent No. 772,775, dated October 18, 1904. Application filed April 12, 1904- Serial No. 202,882. (No specimens.)

To roll wnmn it may concern.-

Be it known that we, WILHELM BEHAGHEL, a subject of the Grand Duke of Baden, and GUSTAV CURT SOHUMANN, a subject of the King of Saxony, doctors of philosophy and chemists, residing at Ludwigshafen-on-the- Rhine, in the Kingdom of Bavaria, German Empire, hay-e invented new and useful Imprdvements in the Production of Indoxylic Compounds, of which the following is a specification.

Our invention relates to improvements in the manufacture of indoxyl and of derivatives of indoxyl.

We have discovered that indoxyl or a derivative thereof is obtained when hydroxyethyl-anilin (GHs. NH. CH1. CI-LOH) or an analogue or a derivative thereof (such as its carboxy derivatives or those which contain an alkyl group attached to the nitrogen atom) is heated with a caustic alkali or with a mixture of caustic alkalies with or without the addition of a water-removing agent, such as an alkaline oxid, or alkaline earth, or alkaline amid, or alkali metal. Instead of the free hydroxyethyl bases their alkali salts may be employed. The indoxyl or derivative thereof so obtained can be transformed in the usual manner or in any'suitable manner into the corresponding indigo coloring-matter.-

The following examples will serve to fur ther illustrate the nature of our invention, which, however, is not limited to these examples. The parts are by weight.

Example 1: Melt together one hundred and thirty-seven (137) parts of hydroxyethyl-anilin and five hundred (500) parts of caustic potash in an autoclave for one (1) hour at a tem-- perature of from two hundred and eighty to two hundred and ninety degrees centigrade, (280 to 290 C.) Dissolve in water the yellow mass so obtained and pass air through the solution and filter ofi the indigo which is precipitated.

Example 2: Heat together in an autoclave one hundred and sixty five (165) parts of ethyl-hydroxyethyl-anilin and five hundred (500) parts of caustic potash for one (1) hour at a temperature of from two hundred and eighty to two hundred and ninety degrees centigrade (280 to 290 C.) and work up the melt in the usual manner.

Example 3: Heat together in an open vessel provided with an inverted condenser one hundred and sixty-five (165) parts of ethylhydroxyethyl-anilin, three hundred and forty (340) parts of burnt lime, and three hundred and forty (340) parts of caustic potash for from one to one and a half (1 to 1%) hours at a temperature of from two hundred and sixty to two hundred and eighty degrees centigrade, (260 to 280 C.)

Example t: Mix together one hundred and eighty-seven (187) parts of the sodium salt of ethyl-hydroxyethyl-anilin, three hundred and forty (340) parts of lime, and one hundred and seventy (170) parts of anhydrous caustic potash and heat the whole to a temperature of from two hundred and seventy to two hundred and seventy-five degrees centigrade, (270 to 275 C.)

Example 5. Heat together onehundred and thirty-seven (137) parts of hydroxyethyl-anilin, seven hundred (700) parts of anhydrous caustic potash, and seventy (70) parts of sodamid at a temperature of from two hundred and fifty to two hundred and seventy degrees centigrade, (250 to 270 0.)

Example 6: Heat together one hundred and sixty-five (165) parts of ethylh,vdroxyethylanilin, sixty-five parts of sodium oxid and seven hundred (700) parts of anhydrous caustic potash at a temperature of from two hundred and fifty to two hundred and seventy degrees centigrade, (250 to 270 C.)

, Example 7: Melt together at atemperature of two and seventy degrees centigrade(270 0.) one hundred and eighty-one (181) parts of dihydroxyethyl-anilin, CoHt-N (CHzCHzO2Hz,) three hundred and sixty (360) parts of caustic potash and three hundred and sixty (360) parts of quick-lime. v

Correction in Letters Patent No. 772,775.

Example 8: 1\Ielt together at a temperature of two hundred and fifty degrees centigrade (250 C.) two hundred and nineteen (219) parts of the sodium salt of hydroxyethyl-ani lin-ortho-carbonic acid and six hundred (600) parts of anhydrous caustic potash.

VVhat We claim is- 1. The process for the production of indoxylic compounds, which consists in heating an aromatic amin, which contains a hydroxyethyl group attached to the amido-nitrogen atom, in an alkaline melt.

2. The process for the production of indoxylic compounds, which consists in heating an aromatic amin, which contains a hydroxyethyl group attached to the amido-nitrogen atom, in an alkaline melt containing a dehydrating agent.

3. The process for the production of indoxylic compounds, which consists in heating an aromatic-amin, which contains a l1 -'Ci1OX ethyl group attached to the amido-nitrogen atom, in a caustic-potash melt.

4:. The process for the production of indoxylic compounds, which consists in heating an aromatic amin, which contains a hydroxyethyl group .attached to the amido-nitrogen atom, in a caustic-potash melt containing a de hydrating agent.

5. The process for the production of indoxylic compounds, which consists in heating [SEAL] l an aromatic amin, which contains a hydroxy- 1 quicklime.

, 6..lhe process i doxylic compounds, which consists in heating hydroxyethhanilin in an alkaline melt.

{ 7. The process for the production of in- 5 doxylic compounds, which consists in heating I hydroxyethyl-anilin in an alkaline melt conl taining a dehydrating agent.

l 8. The process for the production of indoxylic compounds, which consists in heating hyd roxyethyl-anilin in a caustic-potash melt.

9. The process for the production of indoxylic com pounds, which consists in heating hydroxyethyl-anilin in a caustic-potash melt containing a hydrating agent- 10. The process for the production of indoxylic compounds, which consists in heating hydroxyethyl-anilin in a caustic-potash melt containing quicklime.

our hands in the presence of two subscribing witnesses.

VVILHELM BEHAGHEL. GUSTAV GURT SCHUMANN.

Witnesses:

ERNEST F. EHRHARDT, J. ALEC. LLOYD,

It is hereby certified that in Letters Patent N 0. 772,775, granted October 18 1904 upon the application of'Wilhelm Behaghel and Gustav Curt Schumann of Liid 7 shafen-on-the-Rhine, Germany, for an improvement in Processes of Making lndox l Compounds, an error appears in the printed specification requiring correct' y m follows: In line -19, page 2, the word hydrating should read dehydratin a d th the said Letters Patent should be read with this correction therein theft th at may conform to the record of the case in the Patent Ofiice. same Signed and sealed this 31st day of January, A. D1, 1905.

F. I. ALLEN,

Commissioner of Patents.

for the production of in In testimony whereof we have hereunto set Correction in Letters Patent No. 772,775.

Example 8: 1\Ielt together at a temperature of two hundred and fifty degrees centigrade (250 C.) two hundred and nineteen (219) parts of the sodium salt of hydroxyethyl-ani lin-ortho-carbonic acid and six hundred (600) parts of anhydrous caustic potash.

VVhat We claim is- 1. The process for the production of indoxylic compounds, which consists in heating an aromatic amin, which contains a hydroxyethyl group attached to the amido-nitrogen atom, in an alkaline melt.

2. The process for the production of indoxylic compounds, which consists in heating an aromatic amin, which contains a hydroxyethyl group attached to the amido-nitrogen atom, in an alkaline melt containing a dehydrating agent.

3. The process for the production of indoxylic compounds, which consists in heating an aromatic-amin, which contains a l1 -'Ci1OX ethyl group attached to the amido-nitrogen atom, in a caustic-potash melt.

4:. The process for the production of indoxylic compounds, which consists in heating an aromatic amin, which contains a hydroxyethyl group .attached to the amido-nitrogen atom, in a caustic-potash melt containing a de hydrating agent.

5. The process for the production of indoxylic compounds, which consists in heating [SEAL] l an aromatic amin, which contains a hydroxy- 1 quicklime.

, 6..lhe process i doxylic compounds, which consists in heating hydroxyethhanilin in an alkaline melt.

{ 7. The process for the production of in- 5 doxylic compounds, which consists in heating I hydroxyethyl-anilin in an alkaline melt conl taining a dehydrating agent.

l 8. The process for the production of indoxylic compounds, which consists in heating hyd roxyethyl-anilin in a caustic-potash melt.

9. The process for the production of indoxylic com pounds, which consists in heating hydroxyethyl-anilin in a caustic-potash melt containing a hydrating agent- 10. The process for the production of indoxylic compounds, which consists in heating hydroxyethyl-anilin in a caustic-potash melt containing quicklime.

our hands in the presence of two subscribing witnesses.

VVILHELM BEHAGHEL. GUSTAV GURT SCHUMANN.

Witnesses:

ERNEST F. EHRHARDT, J. ALEC. LLOYD,

It is hereby certified that in Letters Patent N 0. 772,775, granted October 18 1904 upon the application of'Wilhelm Behaghel and Gustav Curt Schumann of Liid 7 shafen-on-the-Rhine, Germany, for an improvement in Processes of Making lndox l Compounds, an error appears in the printed specification requiring correct' y m follows: In line -19, page 2, the word hydrating should read dehydratin a d th the said Letters Patent should be read with this correction therein theft th at may conform to the record of the case in the Patent Ofiice. same Signed and sealed this 31st day of January, A. D1, 1905.

F. I. ALLEN,

Commissioner of Patents.

for the production of in In testimony whereof we have hereunto set It is hereby certified that in Letters Patent No. 772,775, granted October 18, 1904, upon the application of Wilhelm Behaghel and Gustav Curt Schumann, of Ludwigshafen-on-the-Rhine, Germany, for an improvement in Processes of Making Indoxylic Compounds, an error appears in the printed specification requiring correction, as follows: In line -19, page 2, the word hydrating should read dehydrating; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 31st day of January, A. D., 1905.

[snub] F. I. ALLEN,

Commissioner of Patents. 

